Non-azo and azo compounds containing at least one 4,6-diamino-1-substituted-5-substituted carbamoylpyrid-2-one group

ABSTRACT

Compounds of the formula ##STR1## wherein each R is independently --N(R 1 ) 2 , --N.sup.⊕ (R 2 ) 3  A.sup.⊖ or hydroxy, wherein 
     each R 1  is independently hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl or aryl or 
     both R 1  &#39;s taken together and with the nitrogen atom to which they are attached form a 5- or 6-membered saturated heterocyclic ring, 
     each R 2  is independently alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl or aryl or 
     two R 2  &#39;s taken together and with the nitrogen atom to which they are attached form a 5- or 6-membered saturated heterocyclic ring or 
     all three R 2  &#39;s taken together and with the nitrogen atom to which they are attached form a 5- or 6-membered unsaturated heterocyclic ring, and 
     A.sup.⊖ is a non-chromophoric anion, 
     each T is independently a bridging radical, and 
     Z is hydrogen or --N═N--D, wherein D is a diazo component radical, 
     are dyes useful for the dyeing of for example, paper, leather, cellulosic materials such as cotton and textiles comprising polyacrylonitrile or polyamides or polyesters modified to contain anionic groups. Polymeric compounds containing at least two units each of which contains residues of two compounds of said formula, which may be the same or different, joined by biscationic bridging radicals are also useful as dyes for the same materials.

According to the invention there is provided compounds of formula I ##STR2## in which

Z is hydrogen or --N═N--D where D is the residue of a diazo component;

each T independently is a bridging group;

each R independently is --N(R₁)₂, --N.sup.⊕ (R₂)₃ A.sup.⊖ or --OH;

where each R₁ independently is hydrogen; alkyl; alkyl substituted by halogen, cyano, hydroxy, phenyl or carbamoyl; cycloalkyl; cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups or aryl;

and each R₂ independently is alkyl; alkyl substituted by halogen, cyano, hydroxy, phenyl or carbamoyl; cycloalkyl; cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups or aryl;

or both R₁ 's or two R₂ 's together with the N-atom to which they are attached form a 5- or 6-membered saturated heterocyclic ring;

or all three R₂ 's together with the N-atom to which they are attached form a 5- or 6-membered unsaturated heterocyclic ring, and

A.sup.⊖ is a non-chromophoric anion.

Preferably Z is Z' where Z' is defined later.

Preferred compounds of formula I are of formula II ##STR3## in which

T₁ is C₁₋₁₂ alkylene which may be interrupted by 1 to 3 heteroatoms or C₃₋₁₂ alkenylene group which may be interrupted by 1 to 3 heteroatoms;

R' is ##STR4## where each R₁ ' independently is hydrogen; C₁₋₁₂ alkyl unsubstituted or substituted by halogen, cyano, hydroxy, unsubstituted phenyl CONH₂ ; phenyl unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups or cyclohexyl unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups; or

both R₁ 's together with the N-atom to which they are attached form an unsubstituted piperidine, unsubstituted morpholine, unsubstituted piperazine, C- unsubstituted N-C₁₋₄ alkylpiperazine or unsubstituted pyrrolidine ring; and

each R₂ ' independently, is C₁₋₁₂ alkyl unsubstituted or substituted by halogen, cyano, hydroxy, unsubstituted phenyl or --CONH₂ ; phenyl unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups or cyclohexyl unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups; or

two R₂ 's together with the N-atom to which they are attached form a C-unsubstituted piperidine, C-unsubstituted morpholine, C-unsubstituted piperazine or C-unsubstituted pyrrolidine,

all three R₂ 's together with the N-atom to which they are attached form a pyridinium ring unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups; or ##STR5## and

Z' is hydrogen, ##STR6## where each R₃ independently is halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or hydrogen; and each R_(3a) independently has a significance of R₃ (independent of R₃) or --NO₂, ##STR7##

X when all R₃ 's are hydrogen is selected from X₁ to X₇₆ where X₁ is a direct bond;

X₂ is a linear or branched C₁₋₄ alkylene group; ##STR8##

each z independently is 0, 1 or 2;

each R₄ independently is halogen, unsubstituted C₁₋₄ alkyl or unsubstituted C₁₋₄ alkoxy;

each R₅ independently is hydrogen or unsubstituted C₁₋₄ alkyl;

each R₆ independently is a linear or branched unsubstituted C₁₋₄ alkylene group;

each R₇ independently is --NH₂, --OH, --NH--CH₂ CH₂ OH, --NH(CH₂)₃ --N(CH₃)₂, --N(CH₂ --CH₂ --OH)₂, --N(CH₃)₂, --N(C₂ H₅)₂, halogen, --NH--(CH₂)₃ --N(C₂ H₅)₂, ##STR9##

each q independently is 1, 2, 3 or 4;

or X when one or more R₃ 's is or are other than hydrogen, is selected from X₁, X₂, X₁₄, X₂₁, X₃₂ and X₃₄ ;

K is a group of the formula ##STR10## where

R_(a) is a significance of R' other than --OH;

each R₈ independently is hydrogen, methyl, methoxy or ethoxy;

R₉ is a group of the formula ##STR11## where

R_(a) is defined above;

R₁₀ and R₁₁ independently of each another are selected from unsubstituted C₁₋₄ alkyl and unsubstituted C₁₋₄ alkoxy;

R₁₂ is hydrogen, unsubstituted C₁₋₄ alkyl, unsubstituted benzyl or unsubstituted phenyl;

R₁₃ is H, --CN, --CONH₂, ##STR12##

R₁₄ is hydrogen, C₁₋₄ alkyl unsubstituted or substituted by one unsubstituted phenyl group, --(CH₂)₂ --CN, --(CH₂)₂ OH, --(CH₂)_(r) --N(R_(1a))₂, --(CH₂)₃ --OCH₃, ##STR13## where

R_(1a) has all the significances of R₁ (including the cyclic significances) except hydrogen and R_(2a) has all the significances of R₂ (including the cyclic significances).

r is 2, 3, 4, 5 or 6;

each R₁₅ independently is hydrogen, unsubstituted C₁₋₄ alkyl, --(CH₂)₃ --OCH₃, --(CH₂)₂ --OH, --(CH₂)₃ --N(CH₃)₂, --(CH₂)₃ N.sup.⊕ (CH₃)₃ A.sup.⊖ or --(CH₂)₃ --N(C₂ H₅)₂ ;

R₁₆ is --OH or --NH₂ ;

R₁₇ is unsubstituted C₁₋₄ alkyl or --CO--R₂₇ ;

R₁₈ is ##STR14##

R₁₉ is --NH--NH₂, ##STR15##

R₂₀ is an unsubstituted C₁₋₄ alkyl group, ##STR16## or --(CH₂)₂ CN;

R₂₁ is an unsubstituted C₁₋₄ alkyl group, --(CH₂)_(m) --N.sup.⊕ (CH₃)₃ A.sup.⊖ or ##STR17##

R₂₂ is ##STR18##

R₂₃, R₂₄ and R₂₅ independently of one another are selected from hydrogen, halogen, unsubstituted C₁₋₄ alkyl, unsubstituted C₁₋₄ alkoxy, --NO₂ and --CN;

R₂₆ is unsubstituted C₁₋₄ alkyl, --CON[(C₁₋₄)alkyl)]₂, --N(C₁₋₄ alkyl)₂, --CONH(C₁₋₄ alkyl), --NH(C₁₋₄ alkyl) or --NH₂ ;

u is 0, 1, or 2;

R₂₇ is --O--R₃₂ or ##STR19##

R₂₈ and R₂₉ independently of each another are hydrogen, halogen, unsubstituted C₁₋₄ alkyl; unsubstituted C₁₋₄ alkoxy, --NO₂, --NH₂ or --NHCOCH₃ ;

R₃₀ is hydrogen or --NH--CO--(CH₂)_(m) --R₃₅ ;

each R₃₁ independently is --NH--(CH₂)_(m) --N(R₁ ')₂ ;

R₃₂ is unsubstituted C₁₋₄ alkyl;

R₃₃ and R₃₄ independently are hydrogen or unsubstituted C₁₋₄ alkyl;

R₃₅ is --N.sup.⊕ (R₂ ')₃ A.sup.⊖ or ##STR20##

p is a number from 1 to 3 inclusive;

each m independently is 1, 2, 3, 4, 5 or 6; and

K_(a) is a coupling component of the acetoacetyl-alkyl or arylamide series, the pyridone series, the diaminopyridine series, the pyrazolone series, the aminopurazole series, the α- or β-naphthol series, the aminophenyl series or the barbituric acid series;

K_(a) is preferably a group of formulae (a), (b), (c) and (e) to (k) above (defined under symbol K).

Preferred compounds of formula II are of formula III ##STR21## where R" is --OH or ##STR22## and Z" is hydrogen, ##STR23## where

R₃ ' is hydrogen, methyl, methoxy or chloro;

R_(3a) ' is hydrogen, Cl, --NO₂, ##STR24##

R_(3b) is hydrogen, Cl, --NO₂ or CH₃ ;

X', when each R₃ ' is hydrogen is selected from X₁, X₅, X₆, X₇, X₁₀, X₁₁, X₁₂, X₁₆, X₁₇, X₂₂, X₂₅, X₂₆, X₂₇, X₃₀, X₃₁, X₄₉, X₅₀, X₅₁, X₅₂, X₅₃, X₅₄, X₅₈, X₅₉, X₆₄ ; or X₂ ' to X₃₄ ^(vi) below: ##STR25##

or X', when one or more R₃ ' is other than hydrogen is X₁, X₂₁ ', X₁₄ ', X₃₂ ", X₂ ', X₂ " or X₃₄ ';

each R₄ ' independently is hydrogen, chlorine, methyl or methoxy;

each R₇ ' independently is Cl, --NH--CH₂ CH₂ OH, --N(CH₂ CH₂ OH)₂, --OH, --NH₂, --NH(CH₂)₃ N(C₂ H₅)₂, ##STR26##

n is an integer from 2 to 6 inclusive;

each R₁ " is hydrogen or unsubstituted, linear or branched C₁₋₄ alkyl;

K' is a group of one of the formula a₁ to k₁ below: ##STR27## in which

R₂ ' is a group of the formula

    --N(R.sub.1 ").sub.2 or N.sup.⊕ (R.sub.2 ").sub.2 R.sub.2b 'A.sup.⊖,

where

each R₂ " independently is C₁₋₄ alkyl; and

R_(2b) ' is methyl, ethyl or benzyl;

R₉ ' is ##STR28##

R₁₀ ' and R₁₁ ' independently of each other are --CH₃, --C₂ H₅, --OCH₃ or --OC₂ H₅ ;

R₁₃ ' is --CN, --CONH₂, ##STR29## or hydrogen;

R₁₄ ' is hydrogen, --CH₃, --C₂ H₅, ##STR30## --(CH₂)₂ --OH, --(CH₂)₃ OCH₃, --(CH₂)₂ --CN, --(CH₂)₃ --N(CH₃)₂, --(CH₂)₃ --N.sup.⊕ (CH₃)₃ A.sup.⊖ or ##STR31##

each R₁₅ ' independently is --CH₂)₂ OH, --(CH₂)₃ OCH₃, --(CH₂)₃ N(CH₃)₂ or --(CH₂)₃ N(C₂ H₅)₂,

R₁₈ ' is ##STR32##

R₁₉ ' is --NH--(CH₂)₃ --N(R₁ ")₂ -- or ##STR33##

R₂₀ ' is --CH₃, C₂ H₅ or ##STR34##

R₂₁ ' is --CH₃, --C₂ H₅, --(CH₂)₂ --N.sup.⊕ (CH₃)₃ A.sup.⊖ or ##STR35##

R₂₂ ' is ##STR36##

each R₂₃ ', R₂₄ ' and R₂₅ ' independently of one another is hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy;

R₃₁ ' is --NH--(CH₂)_(m) --N(CH₃)₂ or --NH--CH₂)_(m) N(C₂ H₅)₂ ;

K_(a) ' is a coupling component of formula (a₁), (b₁), (c₁), (e₁), (f₁), (g₁), (h₁), (i₁) or (k₁) defined under symbol K'.

Preferred compounds of formula III are of formula IV ##STR37## in which

R₃ ' is hydrogen, chloro, methyl or methoxy;

X", when both R₃ ' s are hydrogen, is

X₁, X₁₀, X₁₂, X₁₇, X₂₇, X₅₁, X₅₂, X₅₄, X₆₄, X₂ ', X₂ ", X₁₄ ', X₁₉ ', X₂₀ ', X₁₉ ", X₁₉ "', X₂₀ ", X₂₁ ', X₃₂ ', X₃₂ ", X₃₄ ', X₃₄ ", X₃₄ "', X₃₄ ^(iv), X₃₄ ^(v) or X₃₄ ^(vi) ;

and X", when one R₃ ' is chloro, methyl or methoxy, is a direct bond;

K" is a group of formula (a₁), (b₁), (d₁), (e₁), (f₁), (g₁), (h₁), (i₁), (k₁) or (c₂) ##STR38## where p' is a number from 1 to 2, preferably on average 1.5.

Compounds of formula I where Z is hydrogen may be prepared by cyclising 2 moles of a compound of formula V ##STR39## where the symbols are defined above, in the presence of a substantially water-free organic medium (for example an alcohol) at high temperatures in the presence of a base (for example an alcoholate). The compounds of formula V are known or can be formed by known methods from known compounds.

Compounds of formula I where Z is other than hydrogen can be formed by reacting a diazotised amine of formula VI

    D--NH.sub.2                                                VI

with a compound of formula I where Z is hydrogen.

Compounds of formula I, where Z is ##STR40## can be prepared by reacting 1 mole of a tetrazotised diamine of formula VII ##STR41## with 2 moles of a compound of formula I where Z is hydrogen, or with 1 mole of a compound of formula I where Z is hydrogen and 1 mole of a compound of formula VIII

    H--K                                                       VIII

where K is as defined above other than of formula (a). Compounds of formulae VI, VII and VIII are known or may be prepared by known methods from known compounds.

Coupling can be carried out by known methods for example in aqueous medium at temperatures from -10° C. to room temperature optionally in the presence of a coupling accelerator for example urea or pyridine.

Further, according to the invention there are provided polymers containing at least two recurring units of one of formulae X to XIII ##STR42## in which E is a bridging group E₁ to E₇₀ ##STR43##

r is an integer from 2 to 6 inclusive;

t is an integer 1 to 6 inclusive; ##STR44##

Y_(o) is --(CH₂)_(q) --, --O--, --S--, --CO--, --COO--, --SO₂ --, --SO₂ --O--, --O--SO₂ --O--, --CO--NH--, --NH--CO--NH--, --NH--CS--NH--, --NH-- or ##STR45##

s is an integer from 2 to 10 inclusive;

Q is --C₂ H₄ --, --C₃ H₆ --, --C₆ H₁₂ or ##STR46##

R_(b) is ##STR47## in which case one bond is attached to T and the remaining bond is attached to E of another unit of formula XII or XIII respectively; and the other symbols are as defined earlier in the specification.

Preferably 2 to 25, more preferably 2 to 10 and most preferably 3 to 6 of one of the recurring units of formulae X_(a) to XIII are present in a polymer according to the invention.

Preferred polymers according to the invention are those of formulae X to XIII_(a) ##STR48## or of formula ##STR49## or of formula ##STR50## or of formula ##STR51## in which

T_(1x) is --(CH₂)--_(n) ;

X' is as defined above;

E' is E₂, E₃, E₄, E₆, E₇, E₁₀, E₁₁, E₁₂, E₁₃, E₁₄, E₁₆, E₁₇, E₁₈, E₂₁, E₂₂, E₂₈, E₂₉, E₃₁, E₃₂, E₃₅, E₃₈, E₄₁, E₄₆, E₆₃ or E₇₁ --(CH₂)₂ --, E₇₂ --(CH₂)₃ --, ##STR52## E₇₄ --(CH₂)₄ --, E₇₅ --(CH₂)₅ --, E₇₆ --(CH₂)₆ --, E₇₇ --CH₂ CH₂ --O--CH₂ CH₂ --, ##STR53## E₈₅ --CH₂ --CH₂ --CO--NH--(CH₂)₂ --NH--CO--CH₂ --CH₂ --

R_(b) ' is --N(R₁ ')₂, --N.sup.⊕ (R₂ ')₃ A.sup.⊖ or ##STR54## where the remaining bond is attached to E' of another unit of formula XII_(a) or XIII_(a) respectively;

v is a number from 2 to 25;

and the other symbols are as defined earlier in the specification.

Preferably in polymers of the invention containing recurring units of formulae X_(a) to XIII_(a),

R₁ ' is preferably R₁ ";

R_(b) ' is preferably R_(b) "; where

R_(b) " is --N(R₁ ")₂ or --N.sup.⊕ (R₂ ")₃ A.sup.⊖ or ##STR55## where one bond is attached to T_(1x) and the remaining free-bond is attached to E of another recurring unit;

E' is preferably E" where E" is E₂, E₃, E₄, E₆, E₇, E₁₀, E₁₁, E₁₂, E₁₃, E₁₄, E₁₆, E₂₁, E₂₈, E₂₉, E₃₁, E₇₂, E₇₄ E₇₆, E₇₇, E₇₈, E₇₉, E₈₀, E₈₁ or E₈₅ ; and

X' is preferably X".

Polymers containing at least 2 recurring units of any one of formulae X to XIII can be prepared by reacting a compound of formula XIV

    E--(Hal).sub.2                                             (XIV)

where Hal is a halogen atom,

with the appropriate amount of a corresponding mono or polyazo compound of formula I preferably in an organic medium at room temperature or at a raised temperature in the presence of an acid receptor.

In this specification when T has the significance of an alkylene group this is preferably --(CH₂)_(n) --, more preferably --(CH₂)₂ --.

When R₁ or R₂ has the significance of an alkyl group this is preferably (C₁₋₁₂ alkyl, more preferably (C₁₋₄ alkyl, and most preferably methyl or ethyl.

When R₁₄ has the significance of a substituted alkyl group this is preferably benzyl or phenylethyl.

Unless indicated to the contrary any alkyl group is preferably C₁₋₄ alkyl, more preferably methyl or ethyl, any alkoxy group is C₁₋₄ alkoxy, more preferably ethoxy or methoxy and any halogen present is chlorine or bromine, more preferably the former.

In the compounds of formula I or formula II (where appropriate) and recurring units of formulae X to XIII the preferences for each symbol are given below:

T is preferably T₁, more preferably --(CH₂)_(n) --;

R is preferably R', more preferably R", most preferably --N(R₁ ")₂ ;

R₁ is preferably R₁ ' more preferably R₁ ";

R₂ is preferably R₂ ' more preferably R₂ ";

R₄ is preferably R₄ ';

R₇ is preferably R₇ ';

R₉ is preferably R₉ ';

R₁₀ and R₁₁ are preferably R₁₀ ' and R₁₁ ';

R₁₃ is preferably R₁₃ ';

R₁₄ is preferably R₁₄ ';

R₁₅ is preferably R₁₅ ';

R₁₈ is preferably R₁₈ ';

R₁₉ is preferably R₁₉ ';

R₂₀ is preferably R₂₀ ';

R₂₁ is preferably R₂₁ ';

R₂₂ is preferably R₂₂ ';

R₂₃, R₂₄ and R₂₅ are preferably R₂₃ ', R₂₄ ' and R₂₅ ';

X is preferably X', more preferably X";

K is preferably K', more preferably K";

p is preferably p';

K_(a) is preferably K_(a) ';

E is preferably E' more preferably E".

All the symbols given above are defined earlier in the specification.

In the compounds or polymers according to the invention the anion A.sup.⊖ may be exchanged for other anions, e.g. with the aid of an ion exchanger, or by means of a reaction with salts or acids, optionally in several stages, e.g. by forming the hydroxide or the bicarbonate, or in accordance with German Published Specification No. 2,001,748 or 2,001,816.

The anion A.sup.⊖ is non-chromophoric and may be one which is conventional in basic dyestuff chemistry. The anion A.sup.⊖ is understood to include both organic and inorganic ions, e.g. halide, such as chloride or bromide, sulphate, bisulphate, methyl sulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate or benzoate ions, or complex anions, such as those of zinc chloride double salts, and furthermore the anions of the following acids: boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid, or addition products of orthoboric acid with polyalcohols, e.g. cis-polyols.

The new compounds or polymers according to the invention may be used as dyestuffs or they may be used in the form of aqueous, e.g. concentrated stable solutions or as granules in quaternised form and/or in the form of the corresponding salts of mineral acids or organic acids, for dyeing all types of fibre material, cellulose, cotton or leather, but especially paper or paper products, and also for bast fibres, such as hemp, flax, sisal, jute, coir or straw.

The dyestuffs may also be employed in the production of bulk-dyed, sized and unsized paper. They may be similarly employed for dyeing paper by dipping. Paper, leather and cellulose can be dyed in accordance with known methods.

In paper production, the dyestuffs according to the invention and their preparations do not colour the back water at all, or only slightly which is particularly advantageous for purification of the back water. The dyestuffs according to the invention are highly substantive, do not mottle when dyed on paper, and are substantially insensitive to pH. The dyeings on paper are notable for their good light fastness properties. After long-term exposure to light, the shade alters tone-in-tone. The dyed papers are wet-fast, not only to water, but also to milk, soap water, sodium chloride solutions, fruit juices and sweetened mineral water, and because of their good alcohol fastness, they are also resistant to alcoholic beverages; furthermore, when dyed on paper, they have a very stable shade.

The dyestuffs according to the invention may be used for dyeing, padding or printing polyacrylonitrile textiles, or polyamide or polyester textiles which are modified by anionic groups.

In the following Examples all parts and percentages are by weight and all temperatures are given in degrees Centigrade.

EXAMPLE 1 (a) Preparation of the coupling component of formula ##STR56##

11.3 g of ethyl cyanoacetate are added dropwise whilst cooling to a solution of 10.2 g of dimethylaminopropylamine in 200 ml of absolute ethanol, so that the temperature of the reaction solution remains constantly below 35°. The solution is stirred at 30°-35° until thin-layer chromatography indicates that formation of cyanoacetic acid dimethylaminopropylamide has ceased. Then, 1.7 g of sodium ethylate are added to the solution, which is boiled under reflux for 14 hours. The solvent is then removed under vacuum on a rotary evaporator and the remaining brown oil is taken up in 200 ml of dilute hydrochloric acid. The solution thus obtained can be used as such for dyestuff syntheses.

In the following Table I the composition of further coupling components is given. They may be produced analogously to the method described in Example 1 from suitable starting products and are of formula (Ia) for K₁₂ and K₁₃ or (Ib) for K₁ to K₁₁ and K₁₄ and K₁₅ ##STR57## where in formula I_(b), R is ##STR58## for K₁ to K₁₁ and R is --OH for K₁₄ to K₁₅ :

                                      TABLE I                                      __________________________________________________________________________     Coupling                                                                       Component                                                                      K      R.sub.1   R.sub.2  R.sub.3                                                                               T                                             __________________________________________________________________________     K1     --        CH.sub.3 CH.sub.3                                                                              (CH.sub.2).sub.2                              K2     --        C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       "                                             K3     --        CH(CH.sub.3).sub.2                                                                      CH(CH.sub.3).sub.2                                                                    "                                             K4     --        C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                       "                                             K5     --        H        CH.sub.3                                                                              (CH.sub.2).sub.3                              K6     --        CH.sub.3 "      "                                             K7     --        C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                       "                                             K8     --        "        "      (CH.sub.2).sub.4                              K9     --        "        "                                                                                      ##STR59##                                     K10   --        H        H      (CH.sub.2).sub.3                               K11   --        H        H      (CH.sub.2).sub.2                               K12   CH.sub.3  CH.sub.3 CH.sub.3                                                                               (CH.sub.2).sub.3                              K13                                                                                   ##STR60##                                                                               "        "      "                                              K14   --        --       --     (CH.sub.2).sub.2                               K15   --        --       --     (CH.sub.2).sub.3                              __________________________________________________________________________

EXAMPLE 1(b)

13.8 g of o-nitroaniline are suspended in 200 ml of water, whilst adding 50 ml of 10N hydrochloric acid. 20 ml of a 5N sodium nitrite solution are added dropwise at 0°-5°, over the course of ca. 45 minutes, to the brown suspension. After the addition of the nitrite, unspent nitrous acid is decomposed with aminosulphonic acid. The diazonium salt solution is filtered by adding decolourising carbon, to produce a clear yellow solution. This solution is then added dropwise over 30 minutes at room temperature to a copper solution containing hydrochloric acid and containing 34.5 g of 4,6-diamino-1-(dimethylaminopropyl)-5-(3'-dimethylaminopropyl)-carbamoyl-1,2-dihydropyridin-2-one. During this addition, the pH is kept at between 2 and 3 by adding simultaneously a solution of caustic soda. When coupling has ended, the reaction mixture is rendered alkaline with ammonia solution, the dyestuff suspension is heated for a short time to 60° and allowed to cool to room temperature. After filtration, a dyestuff of the following formula ##STR61## is obtained.

From slightly acidic solutions, this dyestuff dyes polyacrylonitrile, cotton, leather and paper in yellow shades. Because of its good solubility, the dyestuff is especially suitable for the gel-dyeing of polyacrylonitrile.

In Table II further dyestuffs of the formula ##STR62## are given. They may be produced by an analogous method to that described in Example 1b from suitable starting products.

                  TABLE II                                                         ______________________________________                                              Radical K of                                                                   Coupling     Definition and Definition and                                EX.  Component    Position of R.sub.5                                                                           Position of R.sub.6                           No.  No. of Tab. I                                                                               in ring F      in ring F                                     ______________________________________                                          2   K6           H              H                                              3   K6           3-Cl           H                                              4   K6           4-Cl           H                                              5   K6           2-Cl           5-Cl                                           6   K6           2-NO.sub.2     H                                              7   K6           4-NO.sub.2     H                                              8   K6           2-NO.sub.2     4-Cl                                           9   K6           2-Cl           4-NO.sub.2                                    10   K6                                                                                           ##STR63##     H                                             11   K6                                                                                           ##STR64##     H                                             12   K6           4-OCH.sub.3    H                                             13   K1           4-NO.sub.2     H                                             14   K2           2-Cl           5-Cl                                          15   K3           H              H                                             16   K4           H              H                                             17   K5           2-NO.sub.2     H                                             18   K7           2-NO.sub.2     H                                             19   K8           H              H                                             20   K9           H              H                                             21    K10         H              H                                             22    K11         H              H                                             23    K12                                                                                         ##STR65##      H                                            24    K13                                                                                         ##STR66##     H                                             25   K6                                                                                           ##STR67##     3-CH.sub.3                                     25a  K14         2-NO.sub.2     H                                             ______________________________________                                    

EXAMPLE 26

22.7 g of 4,4'-diaminobenzanilide are dissolved in 200 ml of water at 90° with 50 ml of 10N hydrochloric acid. 50 ml of 4N sodium nitrite solutions are added to the suspension which is obtained upon cooling to 0°-5°. After the addition of the nitrite, the unspent nitrous acid is broken down with aminosulphonic acid. The diazonium salt solution is filtered by adding decolourising carbon. The clear solution is added in drops in 30 minutes to a copper solution containing hydrochloric acid, and containing 69 g of 4,6-diamino-1-(dimethylaminopropyl)-5-(N-dimethylaminopropylcarbamoyl)-1,2-dihydropyridin-2-one. During coupling, the pH value is kept at between 2 and 3 by adding simultaneously a solution of caustic soda. When coupling has ended, the reaction mixture is rendered alkaline with ammonia solution, the dyestuff suspension is heated for a short time to 60° and allowed to cool to room temperature. After filtration, a dyestuff of the formula ##STR68## is obtained. From slightly acidic solutions, it dyes polyacrylonitrile, cotton, leather and paper in reddish-yellow shades.

Table III gives the composition of further dyestuffs of the formula ##STR69## and these dyestuffs may be made by a method analogous to that of Example 26.

                                      TABLE III                                    __________________________________________________________________________        Radical K of                                                                              Radical K' of               Definition of X                      EX.                                                                               Coupling Component                                                                        Coupling Component          from the                             No.                                                                               No. of Table I                                                                            No. of Table I              description                          __________________________________________________________________________     27 K6         K6                          X.sub.51                             28 K6         K6                          X.sub.2 '                            29 K6         K6                          X" .sub.2                            30 K6         K6                          X' .sub.34                           31 K6         K6                          X" .sub.34                           32 K6         K6                          X.sub.67 (R.sub.6 =                                                            (CH.sub.2).sub.2)                    33 K6         K6                                                                                                          ##STR70##                                                                     R.sub.6 = (CH.sub.2).sub.2           34 K6         K6                          X.sub.72                             35 K1         K1                          X.sub.11                             36 K2         K2                          X.sub.2 '                            37 K1         K1                          X" .sub.2                            38 K1         K1                          X" .sub.34                           39 K3         K3                          X.sub.67 (as Example 32)             40 K1         K1                          X.sub.67 (as Example 33)             41 K1         K1                          X.sub.72                             42 K4         K4                          X.sub.11                             43 K4         K4                          X.sub.2 '                            44 K4         K4                          X .sub.2"                            45 K4         K4                          X' .sub.34                           46 K5         K5                          X.sub.11                             47 K5         K5                          X.sub.2 '                            48 K5         K5                          X .sub.2"                            49 K5         K5                          X' .sub.34                           50 K7         K7                          X.sub.11                             51 K7         K7                          X.sub.2 '                            52 K7         K7                          X .sub.2"                            53 K7         K7                          X' .sub.34                           54 K8         K8                          X .sub.2"                            55 K8         K8                          X' .sub.34                           56 K9         K9                          X' .sub.34                           57 K9         K9                          X.sub.67 (as Example 32)             58  K10        K10                        X' .sub.34                           59  K10        K10                        X.sub.11                             60  K11        K11                        X' .sub.34                           61  K11        K11                        X" .sub.34                           62  K12        K12                        X' .sub.34                           63  K13        K13                        X' .sub.34                           64 K6         K1                          X' .sub.34                           65 K6         K7                          X' .sub.34                           66 K6         K4                          X' .sub.34                           67 K6         K4                          X.sub.11                             68 K6         K7                          X.sub.11                             69 K6         K1                          X.sub.11                             69a                                                                                K14        K14                        X.sub.11                             __________________________________________________________________________        Radical K of                                                                              Radical K' of                                                    EX.                                                                               Coupling Component                                                                        Coupling Component                                               No.                                                                               No. of Table I                                                                            No. of Table I              X                                    __________________________________________________________________________     70  K12                                                                                       ##STR71##                  X' .sub.34                           71 K6         "                           X.sub.11                             72 K6                                                                                         ##STR72##                  X.sub.11                             73 K6         "                           X' .sub.34                           74 K6                                                                                         ##STR73##                  X' .sub.34                           74a                                                                                K14       "                           X.sub.11                             75 K6         "                           X.sub.11                             76 K6                                                                                         ##STR74##                  X' .sub.34                           77 K6         "                                                                78 K6                                                                                         ##STR75##                  X.sub.11                             79 K6                                                                                         ##STR76##                  X.sub.11                             80 K6                                                                                         ##STR77##                  X.sub.11                             81 K6                                                                                         ##STR78##                  X' .sub.34                           82  K12                                                                                       ##STR79##                  X.sub.11                             83 K6                                                                                         ##STR80##                  X.sub.11                             84 K6                                                                                         ##STR81##                  X.sub.34                             __________________________________________________________________________

EXAMPLE 85

14 g of the dyestuff of Example 26 are stirred into 100 ml of 2-ethoxyethanol, and then 10 ml of 10% caustic soda are added. 2.2 g of α,α-dichloro-p-xylene are then added in small portions at room temperature, over the course of 3 hours, and the mixture is stirred for a further 15 hours at room temperature and for one hour at 35°. The separated dyestuff is filtered off. The resulting polymer contains 3-6 recurring units of the formula ##STR82##

The polymeric dye dyes paper reddish-yellow shades. The dyeings are notable for their particularly good wet fastness properties.

In Table IV polymers containing 3-6 recurring units of formula ##STR83## are shown which can be prepared by a method analogous to that of Example 85.

                  TABLE IV                                                         ______________________________________                                         EXAMPLE                                                                        No.            X      Definition of E                                          ______________________________________                                         86             X.sub.51                                                                              E.sub.10                                                 87             X.sub.2 '                                                                             E.sub.10                                                 88             X.sub.2 "                                                                             E.sub.10                                                 89             X.sub.34 '                                                                            E.sub.10                                                 90             X.sub.34 '                                                                            E.sub.13                                                 91             X.sub.34 '                                                                            E.sub.74                                                 92             X.sub.34 '                                                                            E.sub.11                                                 ______________________________________                                    

EXAMPLES 93 TO 96

In Table V polymers containing recurring units of the formula ##STR84## can be prepared by a method analogous to that of Example 85.

                  TABLE V                                                          ______________________________________                                         EX.                                                                            No.   Definition of E                                                                            D                                                            ______________________________________                                         93    E.sub.10                                                                                    ##STR85##                                                   94    E.sub.13                                                                                    ##STR86##                                                   95    E.sub.74                                                                                    ##STR87##                                                   96    E.sub.11                                                                                    ##STR88##                                                   ______________________________________                                    

EXAMPLES 97 TO 100

In Table VI polymers containing 3 to 6 recurring units of the formula ##STR89## may be prepared by a method analogous to that of Example 85.

                  TABLE VI                                                         ______________________________________                                         EX.                                                                            No.   Definition of E                                                                            D                                                            ______________________________________                                         97    E.sub.10                                                                                    ##STR90##                                                   98    E.sub.13                                                                                    ##STR91##                                                   99    E.sub.74                                                                                    ##STR92##                                                   100   E.sub.11                                                                                    ##STR93##                                                   ______________________________________                                    

EXAMPLES 101 TO 107

In Table VII polymers containing 3 to 6 recurring units of the formula ##STR94## may be prepared by a method analogous to that of Examples 85, from suitable starting materials.

                  TABLE VII                                                        ______________________________________                                         Example No.    X      Definition of E                                          ______________________________________                                         101            X.sub.51                                                                              E.sub.10                                                 102            X.sub.2 '                                                                             E.sub.10                                                 102            X.sub.2 "                                                                             E.sub.10                                                 104            X.sub.34 '                                                                            E.sub.10                                                 105            X.sub.34 '                                                                            E.sub.13                                                 106            X.sub.34 '                                                                            E.sub.74                                                 107            X.sub.34 '                                                                            E.sub.11                                                 ______________________________________                                    

Dyeings on paper made from dyestuffs of Examples 2 to 26 and 28 to 30 are greenish-yellow to orange, from those of Examples 27 and 31 to 84 and from those of Examples 85 to 107 are yellow to yellowish-green.

The significances of X and E in the above Tables are as defined earlier in the specification.

DYEING EXAMPLE A

70 Parts of chemically bleached sulphite cellulose (of pinewood) and 30 parts of chemically bleached sulphite cellulose (of birchwood) are ground in a Hollander in 2000 parts of water. 0.2 Parts of the dyestuff described in Example 26 are sprinkled into this pulp. After mixing for 20 minutes, paper is produced from this pulp. The absorbent paper obtained in this way is dyed reddish-yellow. The waste water is practically colourless.

DYEING EXAMPLE B

0.5 Parts of the dyestuff of Example 26 are dissolved in 100 parts of hot water and cooled to room temperature. This solution is added to 10 parts of chemically bleached sulphite cellulose which have been ground in a Hollander with 2000 parts of water. After thorough mixing for 15 minutes, sizing takes place.

Paper which is produced from this matter has a reddish-yellow shade of average intensity, with good wet fastness properties.

DYEING EXAMPLE C

An absorbent length of unsized paper is drawn through a dyestuff solution of the following composition at 40° to 50°. 0.5 Parts of the dyestuff of Example 26; 0.5 parts of starch and 99.0 parts of water. The excess dyestuff solution is squeezed out through two rollers. The dried length of paper is dyed reddish-yellow with good fastness.

DYEING EXAMPLE D

2 Parts of the dyestuff according to Example 26 are dissolved at 40° in 4000 parts of softened water. 100 Parts of premoistened cotton fabric are entered into the bath, which is heated for 30 minutes to boiling temperature. The bath is kept at boiling temperature for 1 hour, and the water which evaporates is replaced from time to time. The dyeing is then removed from the liquor, rinsed with water and dried. The dyestuff is absorbed practically quantitatively on the fibres; the dye bath is practically colourless. A reddish-yellow dyeing is obtained with good light fastness and good wet fastness.

In Dyeing Examples A to D an appropriate amount of any one of dyestuffs of Examples 1 to 25 and 27 to 107 in liquid or granulate preparation form may be used instead of the amount of the dyestuff of Example 26 to produce good dyeings with good fastness properties. 

What is claimed is:
 1. A compound of the formula ##STR95## wherein each R is independently --N(R₁)₂, --N.sup.⊕ (R₁)₃ A.sup.⊖ or hydroxy, whereineach R₁ is independently hydrogen; C₁₋₁₂ alkyl; C₁₋₁₂ alkyl substituted by halo, cyano, hydroxy, phenyl or carbamoyl; cyclohexyl; cyclohexyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl or phenyl substituted by 1 to 3 C₁₋₄ alkyl groups or --N(R₁)₂ is piperidino, morpholino, piperazino, N'-C₁₋₄ alkylpiperazino or pyrrolidino, each R₂ is independently C₁₋₁₂ alkyl; C₁₋₁₂ alkyl substituted by halo, cyano, hydroxy, phenyl or carbamoyl; cyclohexyl; cyclohexyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl or phenyl substituted by 1 to 3 C₁₋₄ alkyl groups or --N.sup.⊕ (R₂)₃ is N-R₂ -piperidinium, N-R₂ -morpholinium, N-R₂ -piperazinium, N-R₂ -N'-C₁₋₄ alkylpiperazinium, N-R₂ -pyrrolidinium, pyridinium or pyridinium substituted by 1 to 3 C₁₋₄ alkyl groups, wherein R₂ is as defined above, and A.sup.⊖ is a non-chromophoric anion, each T is independently C₁₋₁₂ alkylene or C₃₋₁₂ alkenylene, and Z is hydrogen or --N═N--D, wherein D is a diazo component radical.
 2. A compound according to claim 1 wherein Z is --N═N--D.
 3. A compound according to claim 1 wherein Z is hydrogen.
 4. A compound of the formula ##STR96## wherein each R' Is independently --N(R₁ ')₂, --N.sup.⊕ (R₂ ')₃ A.sup.⊖ or hydroxy, whereineach R₁ ' is independently hydrogen; C₁₋₁₂ alkyl; C₁₋₁₂ alkyl substituted by halo, cyano, hydroxy, phenyl or carbamoyl; cyclohexyl; cyclohexyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl or phenyl substituted by 1 to 3 C₁₋₄ alkyl groups or --N(R₁ ')₂ is piperidino, morpholino, piperazino, N'-C₁₋₄ alkylpiperazino or pyrrolidino, and each R₂ ' is independently C₁₋₁₂ alkyl; C₁₋₁₂ alkyl substituted by halo, cyano, hydroxy, phenyl or carbamoyl; cyclohexyl; cyclohexyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl or phenyl substituted by 1 to 3 C₁₋₄ alkyl groups or --N.sup.⊕ (R₂ ')₃ is N-R₂ '-piperidinium, N-R₂ '-morpholinium, N-R₂ '-piperazinium, N-R₂ '-N'-C₁₋₄ alkylpiperazinium, N-R₂ '-pyrrolidinium, pyridinium or pyridinium substituted by 1 to 3 C₁₋₄ alkyl groups, each T₁ is C₁₋₁₂ alkylene or C₃₋₁₂ alkenylene, and Z' is hydrogen, R1 ? ##STR97## wherein each R₃ is independently hydrogen, halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,each R_(3a) is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro, ##STR98## wherein R₃ is as defined above, and K and X are as defined below, wherein K is ##STR99## wherein K_(a) is ##STR100## wherein each R' and T₁ is as defined above, andeach R_(a), R₈, R₉, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, X and p is as defined below, each R_(a) is --N(R₁ ')₂ or --N.sup.⊕ (R₂ ')₃ A.sup.⊖, R₈ is hydrogen, methyl, methoxy or ethoxy, R₉ is ##STR101## wherein each of R₂₃, R₂₄ and R₂₅ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro or cyano, andR_(a) and R₈ are as defined above, R₁₀ is C₁₋₄ alkyl or C₁₋₄ alkoxy, R₁₁ is C₁₋₄ alkyl or C₁₋₄ alkoxy, R₁₂ is hydrogen, C₁₋₄ alkyl, benzyl or phenyl, R₁₃ is hydrogen, cyano, carbamoyl, ##STR102## wherein R₂₆ is C₁₋₄ alkyl, amino, C₁₋₄ alkylamino, di-(C₁₋₄ alkyl)amino, (C₁₋₄ alkyl)carbamoyl or di-(C₁₋₄ alkyl)carbamoyl, andu is 0, 1 or 2, R₁₄ is hydrogen, C₁₋₄ alkyl, phenyl(C₁₋₄ alkyl), 2-cyanoethyl, 2-hydroxyethyl, --(CH₂)_(r) --N(R_(1a))₂, 3-methoxypropyl, --(CH₂)_(r) --N.sup.⊕ (R₂ ')₃ A.sup.⊖ or phenylamino, whereineach R_(1a) is C₁₋₁₂ alkyl; C₁₋₁₂ alkyl substituted by halo, cyano, hydroxy, phenyl or carbamoyl; cyclohexyl; cyclohexyl substituted by 1 to 3 C₁₋₄ alkyl groups; phenyl or phenyl substituted by 1 to 3 C₁₋₄ alkyl groups or --N(R_(1a))₂ is piperidino, morpholino, piperazino, N'-C₁₋₄ alkylpiperazino or pyrrolidino, and r is 2, 3, 4, 5 or 6, each R₁₅ is independently hydrogen, C₁₋₄ alkyl, 3-methoxypropyl, 2-hydroxyethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl or 3-trimethylammoniumpropyl A.sup.⊖, R₁₆ is hydroxy or amino, R₁₇ is C₁₋₄ alkyl, --CO--OR₃₂ or --CO--NR₃₃ R₃₄, whereinR₃₂ is C₁₋₄ alkyl, R₃₃ is hydrogen or C₁₋₄ alkyl, and R₃₄ is hydrogen or C₁₋₄ alkyl, R₁₈ is ##STR103## wherein each of R₂₈ and R₂₉ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro, amino or acetamido, andR₃₀ is hydrogen or --NH--CO--(CH₂)_(m) --R₃₅, wherein R₃₅ is --N.sup.⊕ (R₂ ')₃ A.sup.⊖, ##STR104## R₁₉ is hydrazino, --NH--(CH₂)_(m) --N(R₁ ')₂ or nitrophenylamino, R₂₀ is C₁₋₄ alkyl, benzyl or 2-cyanoethyl, R₂₁ is C₁₋₄ alkyl, --(CH₂)_(m) --N.sup.⊕ (CH₃)₃ A.sup.⊖ or ##STR105## R₂₂ is ##STR106## wherein each R₃₁ is independently --NH--(CH₂)_(m) --(R₁ ')₂, p is a number from 1 to 3, inclusive, R' and T₁ are as defined above, and X is as defined below, X is a direct bond, linear or branched C₁₋₄ alkylene, ##STR107## wherein R₄ is halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,each R₅ is independently hydrogen or C₁₋₄ alkyl, each R₆ is independently linear or branched C₁₋₄ alkylene, R₇ is hydroxy, halo, amino, dimethylamino, diethylamino, 2-hydroxyethylamino, di-(2-hydroxyethyl)amino, 3-dimethylaminopropropylamino, 3-diethylaminopropylamino, N-methyl-N-phenylamino or N-cyclohexyl-N-methylamino, each q is independently 1, 2, 3 or 4, and each z is independently 0, 1 or 2, with the proviso that when at least one R₃ is other than hydrogen, X is a direct bond, linear or branched C₁₋₄ alkylene, ##STR108## wherein R₅, R₆ and R₇ are as defined above, wherein each A.sup.⊖ is a non-chromophoric anion, each m is independently 1, 2, 3, 4, 5 or 6, and each R₁ ' and R₂ ' is as defined above.
 5. A compound according to claim 4 wherein Z' is ##STR109##
 6. A compound according to claim 4 wherein Z' is hydrogen.
 7. A compound according to claim 4 having the formula ##STR110## wherein each R" is hydroxy or --N(R₁ ")₂,wherein each R₁ " is hydrogen or C₁₋₄ alkyl, Z" is hydrogen, ##STR111## wherein each R₃ ' is independently hydrogen, methyl, methoxy or chloro,R_(3a) ' is hydrogen, chloro, nitro, phenylazo, 3-methylphenylazo, phenoxy, 4-chlorophenoxy or 3-methoxyphenoxy, R_(3b) is hydrogen, chloro, nitro or methyl, and K' and X' are as defined below, and each n is 2, 3, 4, 5 or 6, whereinK' is ##STR112## wherein K_(a) ' is ##STR113## wherein R_(a) ', R₉ ', R₁₃ ', R₁₄ ', R₁₅ ', R₁₆, R₁₈ ', R₁₉ ', R₂₀ ', R₂₁ ', R₂₂ ', X' and p are as defined below, andeach n is 2, 3, 4, 5 or 6, each R_(a) ' is --N(R₁ ")₂ or --N.sup.⊕ (R₂ ")₂ R_(2b) ' A.sup.⊖, whereineach R₂ " is independently C₁₋₄ alkyl, and R_(2b) ' is methyl, ethyl or benzyl, R₉ ' is ##STR114## wherein each of R₂₃ ', R₂₄ ' and R₂₅ ' is independently hydrogen, chloro, methyl, ethyl, methoxy or ethoxy, R₁₀ ' is methyl, ethyl, methoxy or ethoxy, R₁₁ ' is methyl, ethyl, methoxy or ethoxy, R₁₃ ' is hydrogen, cyano, carbamoyl, pyridinium A.sup.⊖, 3-methylpyridinium A.sup.⊖, 3-diethylcarbamoylpyridinium A.sup.⊖, 4-dimethylaminopyridinium A.sup.⊖ or ##STR115## R₁₄ ' is hydrogen, methyl, ethyl, benzyl, 2-phenylethyl, phenylamino, 2-hydroxyethyl, 3-methoxypropyl, 2-cyanoethyl, 3-dimethylaminopropyl, 3-trimethylammoniumpropyl A.sup.⊖ or 3-(N-benzyl-N,N-dimethylammonium)propyl A.sup.⊖, each R₁₅ ' is independently 2-hydroxyethyl, 3-methoxypropyl, 3-dimethylaminopropyl or 3-diethylaminopropyl, R₁₆ is hydroxy or amino, R₁₈ ' is phenyl, ##STR116## R₁₉ ' is --NH--(CH₂)₃ --N(R₁ ")₂ or 4-nitrophenylamino, R₂₀ ' is methyl, ethyl or benzyl, R₂₁ ' is methyl, ethyl, 2-trimethylammoniumethyl A.sup.⊖ or 2-pyridiniumethyl A.sup.⊖, R₂₂ ' is ##STR117## wherein each R₃₁ ' is --NH--(CH₂)_(m) --N(CH₃)₂ or --NH--(CH₂)_(m) --N(C₂ H₅)₂, wherein m is 1, 2, 3, 4, 5 or 6,n is 2, 3, 4, 5, 6, p is a number from 1 to 3, inclusive, and X' is as defined below, and X' is a direct bond, --CH₂ --, --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --S--, --O--, --CH═CH--, --NH--, --NH--CO--, ##STR118## --CH₂ --CO--, --CH═CH--CO--CH═CH-- or --CO--NH--R₆ --CO--NH--,wherein R₄ ' is hydrogen, chloro, methyl or methoxy, R₆ is linear or branched C₁₋₄ alkylene, R₇ ' is hydroxy, chloro, amino, 2-hydroxyethylamino, di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino, N-methyl-N-phenylamino or N-cyclohexyl-N-methylamino, and q is 1, 2, 3 or 4, with the proviso that when at least one R₃ ' is other than hydrogen, X' is a direct bond, --CH₂ --, --(CH₂)₂ --, ##STR119## wherein each A.sup.⊖ is a non-chromophoric anion, and each R₁ " is as defined above.
 8. A compound according to claim 7 having the formula ##STR120## wherein K" is ##STR121## wherein p' is a number from 1 to 2,K_(a) ', R_(a) ', R₉ ', R₁₀ ', R₁₁ ', R₁₃ ', R₁₄ ', R₁₅ ', R₁₆, R₁₈ ', R₁₉ ', R₂₀ ', R₂₁ ' and R₂₂ ' are as defined in claim 7, and R₁ ", X" and n are as defined below, each R₁ " is hydrogen or C₁₋₄ alkyl, each R₃ ' is independently hydrogen, methyl, methoxy or chloro, X" is a direct bond, ##STR122## wherein R₆ is a linear or branched C₁₋₄ alkylene, andR₇ ' is hydroxy, chloro, amino, 2-hydroxyethylamino, di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino, N-methyl-N-phenylamino or N-cyclohexyl-N-methylamino, with the proviso that when at least one R₃ ' is methyl, methoxy or chloro, X" is a direct bond, and each n is 2, 3, 4, 5 or
 6. 9. A compound according to claim 8 wherein each of K" and K_(a) ' is other than ##STR123##
 10. The compound according to claim 7 having the formula ##STR124##
 11. The compound according to claim 7 having the formula ##STR125##
 12. The compound according to claim 7 having the formula ##STR126## 